CN112086703A - Resource treatment method for carbon residue of retired battery - Google Patents
Resource treatment method for carbon residue of retired battery Download PDFInfo
- Publication number
- CN112086703A CN112086703A CN202010947399.XA CN202010947399A CN112086703A CN 112086703 A CN112086703 A CN 112086703A CN 202010947399 A CN202010947399 A CN 202010947399A CN 112086703 A CN112086703 A CN 112086703A
- Authority
- CN
- China
- Prior art keywords
- slag
- leaching
- treatment method
- mixture
- graphite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a resource treatment method of retired battery carbon slag, which comprises the steps of crushing and drying retired battery carbon slag to be treated to obtain fine carbon slag; uniformly mixing the fine carbon slag and the villiaumite to obtain a mixture; then preserving the heat of the mixture for 0.5-4h under the conditions of protective atmosphere and 400 ℃ of 100-; then, the obtained slag is leached out with water or an acidic aqueous solution, then, solid-liquid separation is carried out, and the solid phase is washed with water to obtain leachate and graphite. The method has the advantages of simple process, capability of obtaining the ultra-pure graphite, low roasting temperature, low energy consumption, high treatment efficiency, low environmental pollution, high resource utilization rate, good cycle performance and industrial application prospect.
Description
Technical Field
The invention relates to a resource treatment method of retired battery carbon slag, and belongs to the technical field of harmless and comprehensive utilization of industrial hazardous waste resources.
Background
In recent years, with global strong support for new energy industries, global battery market demand has increased at an alarming rate, with consumer batteries represented by 3C products and power batteries represented by new energy automobiles being most rapidly developed. Along with the continuous expansion of the market scale of new energy automobiles and the demand of energy storage batteries, lithium ion batteries are increased year by year, the quantity of the retired waste lithium ion batteries is increased rapidly, and if the retired batteries are not processed and recycled in time, the huge waste of resources and the serious pollution to the environment are inevitably caused. At present, the recovery technology for the retired battery mainly focuses on extracting valuable metal elements in a positive-negative electrode mixture by adopting a wet leaching process, during the process, carbon slag in which graphite slag and part of unreacted positive electrode residues are mixed together is generated, and because the components of the carbon slag are relatively complex, an effective recovery treatment method is not available at present, the carbon slag can be generally treated only by adopting a stacking or landfill mode, so that the resource is wasted, and the environment pollution is also brought. Aiming at the industrial problem of the treatment and recovery of the carbon residue of the retired battery, experts and scholars in the industry and production line personnel conduct various exploration research.
Researching the recovered carbon of the waste lithium iron phosphate battery by the virtuous and faithful plum trees, regenerating the recovered carbon into a graphite negative electrode material by two modification methods of gas-phase oxidation and glucose pyrolytic carbon coating on the recovered carbon, oxidizing for 3 hours at 550 ℃ in an air atmosphere, and enabling the irreversible capacity of the first circle of the carbon material to be changed from 186 mAhg before modification-1Reduced to 61.1 mAhg-1And the coulomb efficiency of the first circle is improved from 64.4% to 86.9%. Coating the gas-phase modified carbon by liquid-phase impregnation method with glucose as carbon source at 1C (372 mAg)-1) At the current density of (2), the reversible capacity of the composite material circulates 270 circles and is changed from 308.8 mAhg before modification-1 Increased to 424.7 mAhg-1The capacity retention rate is improved from 78.0% to 97.8%, the cycling stability under high current density is obviously improved, the high-rate charge-discharge performance is also obviously improved, but impurities in the carbon slag cannot be effectively removed (Lisong xian. waste lithium iron phosphate battery recycled carbon modification and electrochemical performance research thereof [ D]Middle and south university, 2020).
Chinese patent specification CN105552468A discloses a method for recovering waste lithium ion battery graphite cathode materials, which comprises the steps of sequentially performing alkali liquor soaking, acid liquor soaking and deionized water rinsing pretreatment on a cathode plate separated from a lithium ion battery, then performing pre-roasting, crushing and screening in an air atmosphere with the temperature of 300-plus-500 ℃ to obtain a cathode active substance, then performing wet ball milling mixing on the obtained cathode active substance and oxalate, performing high-temperature treatment at the temperature of 450-plus-800 ℃ in an inert atmosphere, and then cooling, crushing and screening to obtain the battery-grade graphite cathode material.
Chinese patent specification CN103618120B discloses a method for separating and recovering graphite and copper sheets in waste lithium ion battery negative electrode materials, which comprises the steps of soaking the waste negative electrode materials in dilute acid, sieving, adding hydrogen peroxide into the soaking solution to oxidize, filter, wash and dry the obtained product to obtain a preliminarily purified graphite product, and then carrying out high-temperature treatment by a two-step method to obtain high-carbon graphite.
Chinese patent specification CN110835682A discloses a method for cooperatively treating positive and negative active materials of waste lithium ion batteries, which comprises the steps of adding a proper amount of concentrated sulfuric acid into a mixture of the positive active material and the negative active material obtained by crushing and separating the waste lithium ion batteries, carrying out reaction and curing to obtain a cured clinker, leaching the cured clinker with water or dilute acid, carrying out sedimentation separation on leached ore pulp to obtain a leachate containing useful metal elements such as cobalt, lithium, nickel and titanium, and carrying out centrifugal classification on the leached slag to obtain high-quality graphite and residue, thereby realizing cooperative strengthening treatment of the positive and negative active materials in the waste lithium ion batteries.
Chinese patent specification CN107964593A discloses a method for recovering lithium in discarded lithium battery slag by chloridizing, roasting and evaporating, wherein crushed lithium slag is uniformly mixed with a certain amount of metal chloride, and then the mixed lithium slag and metal chloride are roasted under the high-temperature condition that the molar ratio is 1:1-1:2 and the roasting temperature is 800-1200 ℃, so that lithium in the lithium slag is transferred into a gas phase removal system in the form of lithium chloride, and the problem that lithium is difficult to recover in pyrometallurgical treatment of discarded lithium batteries is solved, but new impurity elements are introduced in the processing process, so that the recovery of high-quality graphite is difficult.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a resource treatment method of retired battery carbon slag, which solves the problem that high-purity graphite is difficult to obtain in the prior art.
The technical scheme adopted by the invention is as follows:
a resource treatment method of retired battery carbon slag, wherein the retired battery carbon slag mainly comprises C, Si, Ni, Co and Mn; the method comprises the following steps:
s1, crushing and drying the carbon slag of the retired battery to be treated to obtain fine carbon slag;
s2, uniformly mixing the fine carbon residue obtained in the step S1 with fluorine salt to obtain a mixture; optionally, mixing by using an impregnation method or a mechanical mixing method, preferably a mechanical mixing method;
wherein, the fluorine salt is one or more of sodium fluoride, potassium fluoride, ammonium fluoride, aluminum fluoride and ammonium bifluoride;
s3, preserving the temperature of the mixture obtained in the step S2 for 0.5-4h under the conditions of protective atmosphere and 400 ℃ of 100-;
s4, leaching the slag obtained in the step S3 in water or an acidic aqueous solution, then carrying out solid-liquid separation, and washing a solid phase substance to obtain a leaching solution and graphite;
wherein the purity of the graphite is not less than 99.99%.
Further, in S1, the particle size of the fine carbon residue was less than 150 μm (-100 mesh).
Further, in S2, the fine carbon residue and the fluorine salt are uniformly mixed according to the mass ratio of 1:0.1-3 to obtain a mixed material, and preferably, the fine carbon residue and the fluorine salt are uniformly mixed according to the mass ratio of 1: 0.5-1.5.
Preferably, in S2, the fluorine salt is ammonium fluoride. The adoption of the ammonium fluoride can meet the phase conversion requirement of impurity elements in the carbon slag, and the ammonium fluoride which does not participate in the reaction can be acidic in the subsequent solution leaching stage, which is favorable for the dissolution and separation of lithium fluoride, cobalt fluoride, nickel fluoride and manganous fluoride in the slag, and in addition, under the condition, the aluminum in the slag can be converted into ammonium hexafluoroaluminate which is easily dissolved in water and acid, so that under the condition of adopting the ammonium fluoride, the water can be directly used in the leaching stage, the C and the Al can be effectively separated, and the treatment cost can be favorably reduced.
Further, in S3, the mixture is subjected to heat preservation for 2-4h under the conditions of protective atmosphere and 300 ℃ at 150 ℃ to obtain slag charge and flue gas.
Further, in S4, the acidic aqueous solution contains HCl and HNO3、HF、H2SO4One or more of them.
Optionally, the acidic aqueous solution is one or more of hydrochloric acid, nitric acid, hydrofluoric acid and sulfuric acid.
Further, the concentration of the acid in the acidic aqueous solution is 1 to 22mol/L, further 4 to 18 mol/L.
Further, in S4, the solid-liquid mass ratio is 1:5-30, preferably 1: 10-20 during leaching treatment; optionally, the leaching temperature is 20-100 ℃, preferably 40-80 ℃, and the leaching time is 1-4h, preferably 2-3 h.
Further, introducing the flue gas obtained in S3 into the leachate obtained in S4, and controlling the pH value of the leachate to be 6-10, and further 7-9; adding precipitant into the leachate, and reacting at 30-100 deg.C (preferably 40-60 deg.C) for 0.5-3 hr (preferably 1-2 hr) to obtain waste liquid and metal precipitate, further, the metal precipitate comprises precipitate of Li, Ni, Co, and Mn. Therefore, valuable metals can be enriched, and the valuable metals can be conveniently recovered and treated subsequently.
Further, the precipitant is one or more of ammonium carbonate, ammonium oxalate, oxalic acid and carbonic acid, preferably ammonium carbonate. Further, the addition amount of the precipitant is 1 to 2 times, preferably 1.1 to 1.4 times the total molar amount of lithium, nickel, cobalt, and manganese in the leachate.
Further, the pH value of the waste liquid is adjusted to 3-7, preferably 3-5, and then the waste liquid is sequentially cooled, crystallized, centrifugally separated and dried to obtain the villiaumite. Optionally, the drying is air drying. The residual liquid after cooling and crystallizing the waste liquid can be returned to S4 for recycling and leaching.
Further, adding acid into the waste liquid to adjust the pH value of the waste liquid; the acid is at least one of sulfuric acid, hydrofluoric acid and hydrochloric acid, and preferably hydrofluoric acid.
Furthermore, the retired battery is one or more of a cobalt acid lithium battery, a nickel acid lithium battery, a manganese acid lithium battery and a ferric phosphate lithium battery.
Further, the protective atmosphere is at least one of nitrogen, helium and argon, and preferably nitrogen.
Furthermore, the carbon slag of the retired battery contains 80-90wt% of fixed carbon, 5-10 wt% of volatile components and 2-8 wt% of ash. Wherein, the ash content (wt%) of main elements: 10-14 parts of Si, 25-30 parts of Ni, 15-20 parts of O, 6-10 parts of Mn, 4-8 parts of Co, 4-8 parts of Al, 2-7 parts of Na, 2-6 parts of Fe, 1-6 parts of P, 1-5 parts of Zr and 1-4 parts of Cu.
Compared with the prior art, the invention has the following beneficial effects:
1. the carbon residue of the retired battery is mixed with the villiaumite and then roasted at low temperature, so that the reconstruction and the rapid transfer of non-carbon element phases such as lithium, nickel, cobalt, manganese, Si, Al and the like can be realized, the aluminosilicate can be effectively removed, valuable metals can be converted into soluble metal salts, the leaching toxicity of the product can be ignored, and the recycling and the harmlessness of hazardous waste products can be realized;
2. by adopting the low-temperature roasting and leaching process, the production cost of an enterprise is greatly reduced, the reaction time is shortened, and the impurity removal efficiency is improved.
3. The purity of the graphite obtained by the method is up to more than 99.99 percent, the graphite can completely meet the requirements of new energy graphite cathode materials on purity and particle size, and valuable metal elements such as lithium, nickel, cobalt, manganese and the like in the carbon residue can be simultaneously recovered, so that the efficient recovery and cyclic utilization of the materials are realized.
4. The method has the advantages of simple process, low roasting temperature, low energy consumption, high treatment efficiency, low environmental pollution, high resource utilization rate, good cycle performance and industrial application prospect.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Fig. 2 is an XRD spectrum of the graphite powder obtained in example 2 of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Example 1
Taking 50g of domestic ex-service lithium ion battery carbon residue, wherein the content of fixed carbon is 86.18wt%, the content of volatile matter is 7.98wt%, and the content of ash is 5.84 wt%. Ash content (wt%): si 12.84, Ni 27.50, O18.61, Mn 8.63, Co 6.13, Al 5.96, Na 4.48, Fe 4.23, P3.87, Zr 3.29 and Cu 2.13. Crushing the carbon residue to-150 um (-100 meshes) and NH4F, mechanically and uniformly mixing the materials according to the mass ratio of 1:0.5, then placing the mixture into a corundum crucible, preserving heat for 4 hours at 200 ℃ in an argon atmosphere in a muffle furnace, cooling, and carrying out water bath stirring leaching on slag materials, wherein the leaching temperature is as follows: leaching at 60 ℃ for 1h, and the liquid-solid ratio is 15: 1. Washing the water immersion slag to be neutral, filtering, drying the filter residue, and testing according to a graphite chemical analysis method (GB/T-2008) to obtain the ultrapure graphite powder with the purity of 99.990%.
After the pH of the leachate is controlled to be 9 by introducing flue gas, adding a catalyst which is mixed with the leachate in a molar ratio of 1: 1.2, leaching the ammonium carbonate at the leaching temperature of 60 ℃ for 2 hours, washing, filtering and drying to obtain a cobalt-nickel-manganese mixed product, wherein the recovery rates of lithium, cobalt, nickel and manganese are respectively as high as 95%, 98%, 99% and 89%, HF is added into the wastewater, the PH is controlled to be 4, then, the wastewater is cooled, crystallized, centrifugally separated, dried by airflow, recycled and regenerated to obtain villiaumite, and the supernatant is recycled for the wet leaching process.
Example 2
50g of domestic ex-service lithium ion battery carbon residue is taken, the fixed carbon content is 86.18wt%, the volatile matter content is 7.98wt%, and the ash content is 5.84 wt%. Ash content (wt%): si 12.84, Ni 27.50, O18.61, Mn 8.63, Co 6.13, Al 5.96, Na 4.48, Fe 4.23, P3.87, Zr 3.29 and Cu 2.13. Crushing the carbon residue to-150 um (-100 meshes) and NH4F according to 1:1Mechanically and uniformly mixing the components in a mass ratio, then placing the mixture into a corundum crucible, preserving heat for 4 hours at 250 ℃ in an argon atmosphere in a muffle furnace, cooling, and carrying out water bath stirring leaching on the obtained slag, wherein the leaching temperature is as follows: leaching at 60 ℃ for 1h, and the liquid-solid ratio is 15: 1. Washing the water leaching residue to be neutral, filtering, drying the filter residue, and testing according to a graphite chemical analysis method (GB/T-2008) to obtain the ultrapure graphite powder with the purity of 99.992%, wherein an XRD (X-ray diffraction) spectrum of the obtained graphite powder is shown in figure 2.
After the pH of the leachate is controlled to be 9 by introducing flue gas, adding a catalyst which is mixed with the leachate in a molar ratio of 1: 1.1, taking ammonium carbonate as a precipitator, leaching for 1h at the leaching temperature of 50 ℃, washing, filtering and drying to obtain a cobalt-nickel-manganese mixed product, controlling the recovery rates of lithium, cobalt, nickel and manganese to be respectively as high as 94%, 97%, 98% and 90%, adding HF into wastewater, controlling the pH to be 4, cooling, crystallizing, centrifugally separating, drying by air flow, circularly regenerating to obtain villiaumite, and recycling the supernatant for the wet leaching process.
Example 3
50g of domestic ex-service lithium ion battery carbon residue is taken, the fixed carbon content is 86.18wt%, the volatile matter content is 7.98wt%, and the ash content is 5.84 wt%. Ash content (wt%): si 12.84, Ni 27.50, O18.61, Mn 8.63, Co 6.13, Al 5.96, Na 4.48, Fe 4.23, P3.87, Zr 3.29 and Cu 2.13. Crushing the carbon slag to-150 um (-100 meshes), mechanically and uniformly mixing the carbon slag with NH4F according to the mass ratio of 1:0.7, then placing the mixture into a corundum crucible, roasting the mixture at 200 ℃ in an argon atmosphere in a muffle furnace for 3 hours, cooling, and then carrying out water bath stirring leaching on the obtained slag, wherein the leaching temperature is as follows: leaching for 2h at 70 ℃ and the liquid-solid ratio is 20: 1. Washing the water immersion slag to be neutral, filtering, drying the filter residue, and testing according to a graphite chemical analysis method (GB/T-2008) to obtain the ultrapure graphite powder with the purity of 99.996%.
After the pH of the leachate is controlled to be 9 by introducing flue gas, adding a catalyst which is mixed with the leachate in a molar ratio of 1: 1.2, taking ammonium carbonate as a precipitator, leaching for 1h at the leaching temperature of 60 ℃, washing, filtering and drying to obtain a cobalt-nickel-manganese mixed product, controlling the recovery rates of lithium, cobalt, nickel and manganese to be respectively 93%, 97%, 99% and 85%, adding HF into the wastewater, controlling the pH to be 4, cooling, crystallizing, centrifugally separating, drying by air flow, circularly regenerating to obtain villiaumite, and recycling the supernatant for the wet leaching process.
Example 4
50g of domestic ex-service lithium ion battery carbon residue is taken, the fixed carbon content is 86.18wt%, the volatile matter content is 7.98wt%, and the ash content is 5.84 wt%. Ash content (wt%): si 12.84, Ni 27.50, O18.61, Mn 8.63, Co 6.13, Al 5.96, Na 4.48, Fe 4.23, P3.87, Zr 3.29 and Cu 2.13. Crushing the carbon residue to-150 um (-100 meshes) and NH4F, mechanically and uniformly mixing the materials according to the mass ratio of 1:0.7, then placing the mixture into a corundum crucible, preserving the heat for 4 hours at 300 ℃ in an argon atmosphere in a muffle furnace, cooling, and carrying out water bath stirring leaching on the obtained slag, wherein the leaching temperature is as follows: leaching for 3 hours at 70 ℃ and the liquid-solid ratio is 20: 1. Washing the water immersion slag to be neutral, filtering, drying the filter residue, and testing according to a graphite chemical analysis method (GB/T-2008) to obtain the ultra-pure graphite powder with the purity of 99.991%.
After the pH of the leachate is controlled to be 9 by introducing flue gas, adding a catalyst which is mixed with the leachate in a molar ratio of 1: 1.4, taking ammonium carbonate as a precipitator, leaching for 3 hours at the leaching temperature of 60 ℃, washing, filtering and drying to obtain a cobalt-nickel-manganese mixed product, controlling the recovery rates of lithium, cobalt, nickel and manganese to be respectively 97%, 99% and 92%, adding HF into the wastewater, controlling the pH to be 4, cooling, crystallizing, centrifugally separating, drying by air flow, circularly regenerating to obtain villiaumite, and recycling the supernatant for the wet leaching process.
Example 5
50g of domestic ex-service lithium ion battery carbon residue is taken, the fixed carbon content is 86.18wt%, the volatile matter content is 7.98wt%, and the ash content is 5.84 wt%. Ash content (wt%): si 12.84, Ni 27.50, O18.61, Mn 8.63, Co 6.13, Al 5.96, Na 4.48, Fe 4.23, P3.87, Zr 3.29 and Cu 2.13. Crushing the carbon slag to-150 um (-100 meshes), mechanically and uniformly mixing the carbon slag with NH4F according to the mass ratio of 1:1, then placing the mixture into a corundum crucible, preserving the temperature for 4 hours at 200 ℃ in an argon atmosphere in a muffle furnace, cooling, and then carrying out acid impurity removal on the obtained slag in a sulfuric acid solution, wherein the leaching temperature of sulfuric acid leaching is as follows: leaching at 60 ℃ for 1h, and the liquid-solid ratio is 15: 1. Washing the acid leaching residue to be neutral, filtering, drying the filter residue, and testing according to a graphite chemical analysis method (GB/T-2008) to obtain the ultrapure graphite powder with the purity of 99.996%.
After the pH of the leachate is controlled to be 8 by introducing flue gas, adding a catalyst which is mixed with the leachate in a molar ratio of 1: 1.1, taking ammonium carbonate as a precipitator, leaching for 3 hours at the leaching temperature of 60 ℃, washing, filtering and drying to obtain a cobalt-nickel-manganese mixed product, controlling the recovery rates of lithium, cobalt, nickel and manganese to be respectively 96%, 98%, 99% and 90%, adding HF into wastewater, controlling the pH to be 4, cooling, crystallizing, centrifugally separating, drying by air flow, circularly regenerating to obtain villiaumite, and recycling the supernatant for the wet leaching process.
Example 6
50g of domestic ex-service lithium ion battery carbon residue is taken, the fixed carbon content is 86.18wt%, the volatile matter content is 7.98wt%, and the ash content is 5.84 wt%. Ash content (wt%): si 12.84, Ni 27.50, O18.61, Mn 8.63, Co 6.13, Al 5.96, Na 4.48, Fe 4.23, P3.87, Zr 3.29 and Cu 2.13. Crushing the carbon slag to-150 um (-100 meshes), mechanically and uniformly mixing the carbon slag with NH4F according to the mass ratio of 1:0.7, then placing the mixture into a corundum crucible, preserving the heat for 3 hours at 250 ℃ in an argon atmosphere in a muffle furnace, cooling, and then carrying out acid impurity removal on the obtained slag material in a sulfuric acid solution, wherein the leaching temperature of sulfuric acid leaching is as follows: leaching for 2h at 70 ℃ and the liquid-solid ratio is 20: 1. Washing the acid leaching residue to be neutral, filtering, drying the filter residue, and testing according to a graphite chemical analysis method (GB/T-2008) to obtain the ultrapure graphite powder with the purity of 99.995%.
After the pH of the leachate is controlled to be 8 by introducing flue gas, adding a catalyst which is mixed with the leachate in a molar ratio of 1: 1.2, taking ammonium carbonate as a precipitator, leaching for 3 hours at the leaching temperature of 60 ℃, washing, filtering and drying to obtain a cobalt-nickel-manganese mixed product, controlling the recovery rates of lithium, cobalt, nickel and manganese to be respectively as high as 94%, 97%, 99% and 90%, adding HF into wastewater, controlling the pH to be 4, cooling, crystallizing, centrifugally separating, drying by air flow, circularly regenerating to obtain villiaumite, and recycling the supernatant for the wet leaching process.
The foregoing examples are set forth to illustrate the present invention more clearly and are not to be construed as limiting the scope of the invention, which is defined in the appended claims to which the invention pertains, as modified in all equivalent forms, by those skilled in the art after reading the present invention.
Claims (10)
1. A resource treatment method of retired battery carbon slag, wherein the retired battery carbon slag mainly comprises C, Si, Ni, Co and Mn; the method is characterized by comprising the following steps:
s1, crushing and drying the carbon slag of the retired battery to be treated to obtain fine carbon slag;
s2, uniformly mixing the fine carbon residue obtained in the step S1 with fluorine salt to obtain a mixture;
wherein, the fluorine salt is one or more of sodium fluoride, potassium fluoride, ammonium fluoride, aluminum fluoride and ammonium bifluoride;
s3, preserving the temperature of the mixture obtained in the step S2 for 0.5-4h under the conditions of protective atmosphere and 400 ℃ of 100-;
s4, leaching the slag obtained in the step S3 in water or an acidic aqueous solution, then carrying out solid-liquid separation, and washing a solid phase substance to obtain a leaching solution and graphite;
wherein the purity of the graphite is not less than 99.99%.
2. The recycling method according to claim 1, wherein in S1, the particle size of the fine carbon residue is less than 150 μm.
3. A resource treatment method according to claim 1, characterized in that in S2, the fine carbon residue and the villiaumite are uniformly mixed according to the mass ratio of 1:0.1-3 to obtain a mixture.
4. The method according to claim 1, wherein the fluorine salt is ammonium fluoride in S2.
5. The resource treatment method as claimed in claim 1, wherein in S3, the mixture is subjected to heat preservation for 2-4h under the conditions of protective atmosphere and 300 ℃ of 150 ℃ to obtain slag charge and flue gas.
6. The method according to claim 1, wherein the acidic aqueous solution contains HCl and HNO in S43、HF、H2SO4One or more of them.
7. The method according to claim 1, wherein the acid concentration in the acidic aqueous solution is 1 to 22 mol/L.
8. The resource treatment method according to claim 1, wherein in S4, the solid-liquid mass ratio is 1:5-30 during the leaching treatment;
the leaching temperature is 20-100 ℃, and the leaching time is 1-4 h.
9. A resource treatment method according to any one of claims 1 to 8, characterized in that the flue gas obtained in S3 is introduced into the leachate obtained in S4, and the pH of the leachate is controlled to 8 to 9; adding a precipitator into the leachate, and reacting at 30-100 ℃ for 0.5-3h to obtain waste liquid and metal precipitate;
wherein, the precipitant is one or more of ammonium carbonate, ammonium oxalate, oxalic acid and carbonic acid.
10. A resource treatment method according to claim 9, characterized in that the PH of the waste liquid is adjusted to 3 to 7, and then the waste liquid is sequentially cooled, crystallized, centrifugally separated and dried to obtain the fluorine salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010947399.XA CN112086703B (en) | 2020-09-10 | 2020-09-10 | Resource treatment method for carbon residue of retired battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010947399.XA CN112086703B (en) | 2020-09-10 | 2020-09-10 | Resource treatment method for carbon residue of retired battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112086703A true CN112086703A (en) | 2020-12-15 |
| CN112086703B CN112086703B (en) | 2021-08-06 |
Family
ID=73731723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010947399.XA Active CN112086703B (en) | 2020-09-10 | 2020-09-10 | Resource treatment method for carbon residue of retired battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112086703B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113942999A (en) * | 2021-10-12 | 2022-01-18 | 南京恒泰环保科技有限公司 | Method for recycling graphite from lithium battery cathode carbon powder and preparation method of graphene oxide |
| CN114920226A (en) * | 2022-04-24 | 2022-08-19 | 湖南裕能新能源电池材料股份有限公司 | Method for removing aluminum and copper impurities from phosphorus-iron slag after lithium extraction of lithium iron phosphate battery |
| CN115304059A (en) * | 2022-07-06 | 2022-11-08 | 中南大学 | Recycling treatment method for retired battery carbon slag |
| CN116081621A (en) * | 2023-02-21 | 2023-05-09 | 贵州师范大学 | Method for recycling carbonaceous materials in aluminum electrolysis carbon-containing waste |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534236A (en) * | 2012-02-20 | 2012-07-04 | 武汉科技大学 | Method for recovering valuable metal from metallurgical slag materials |
| CN204760509U (en) * | 2015-07-03 | 2015-11-11 | 阳江市联邦金属化工有限公司 | Processing apparatus of battery waste material carbon sediment |
| CN107623152A (en) * | 2017-10-26 | 2018-01-23 | 江西理工大学 | Applying waste lithium ionic electrokinetic cell resource recycle method |
| CN107964593A (en) * | 2017-11-28 | 2018-04-27 | 北京科技大学 | A kind of method that lithium in lithium cell slag is scrapped by chloridising roasting evaporation recycling |
| CN108130427A (en) * | 2016-12-01 | 2018-06-08 | 铜山县超特有色金属添加剂厂 | A kind of smokeless slag-cleaning agent and preparation method thereof |
| KR20180065471A (en) * | 2016-12-08 | 2018-06-18 | (주)엔에이치리사이텍컴퍼니 | A treatment method of a used lithium battery and a resource recycling system used therefor |
| US20200115774A1 (en) * | 2017-07-21 | 2020-04-16 | Larry Lien | Recovery of lithium from an acid solution |
| CN111137883A (en) * | 2020-01-09 | 2020-05-12 | 成都理工大学 | Method for preparing high-purity graphite from natural graphite |
| CN111430831A (en) * | 2020-03-11 | 2020-07-17 | 中南大学 | Method for recovering waste lithium ion battery negative electrode material |
| CN111430830A (en) * | 2020-03-11 | 2020-07-17 | 中南大学 | Method for recovering valuable components in positive electrode of waste lithium battery based on molten salt system |
| CN111534697A (en) * | 2020-06-09 | 2020-08-14 | 中国恩菲工程技术有限公司 | Selection-smelting combined comprehensive recovery method and device for waste lithium ion batteries |
-
2020
- 2020-09-10 CN CN202010947399.XA patent/CN112086703B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534236A (en) * | 2012-02-20 | 2012-07-04 | 武汉科技大学 | Method for recovering valuable metal from metallurgical slag materials |
| CN204760509U (en) * | 2015-07-03 | 2015-11-11 | 阳江市联邦金属化工有限公司 | Processing apparatus of battery waste material carbon sediment |
| CN108130427A (en) * | 2016-12-01 | 2018-06-08 | 铜山县超特有色金属添加剂厂 | A kind of smokeless slag-cleaning agent and preparation method thereof |
| KR20180065471A (en) * | 2016-12-08 | 2018-06-18 | (주)엔에이치리사이텍컴퍼니 | A treatment method of a used lithium battery and a resource recycling system used therefor |
| US20200115774A1 (en) * | 2017-07-21 | 2020-04-16 | Larry Lien | Recovery of lithium from an acid solution |
| CN107623152A (en) * | 2017-10-26 | 2018-01-23 | 江西理工大学 | Applying waste lithium ionic electrokinetic cell resource recycle method |
| CN107964593A (en) * | 2017-11-28 | 2018-04-27 | 北京科技大学 | A kind of method that lithium in lithium cell slag is scrapped by chloridising roasting evaporation recycling |
| CN111137883A (en) * | 2020-01-09 | 2020-05-12 | 成都理工大学 | Method for preparing high-purity graphite from natural graphite |
| CN111430831A (en) * | 2020-03-11 | 2020-07-17 | 中南大学 | Method for recovering waste lithium ion battery negative electrode material |
| CN111430830A (en) * | 2020-03-11 | 2020-07-17 | 中南大学 | Method for recovering valuable components in positive electrode of waste lithium battery based on molten salt system |
| CN111534697A (en) * | 2020-06-09 | 2020-08-14 | 中国恩菲工程技术有限公司 | Selection-smelting combined comprehensive recovery method and device for waste lithium ion batteries |
Non-Patent Citations (1)
| Title |
|---|
| 张亚楠等: "铝电解炭渣资源化综合利用研究现状", 《世界有色金属》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113942999A (en) * | 2021-10-12 | 2022-01-18 | 南京恒泰环保科技有限公司 | Method for recycling graphite from lithium battery cathode carbon powder and preparation method of graphene oxide |
| CN114920226A (en) * | 2022-04-24 | 2022-08-19 | 湖南裕能新能源电池材料股份有限公司 | Method for removing aluminum and copper impurities from phosphorus-iron slag after lithium extraction of lithium iron phosphate battery |
| CN115304059A (en) * | 2022-07-06 | 2022-11-08 | 中南大学 | Recycling treatment method for retired battery carbon slag |
| CN115304059B (en) * | 2022-07-06 | 2023-11-21 | 中南大学 | Recycling treatment method for retired battery carbon residue |
| CN116081621A (en) * | 2023-02-21 | 2023-05-09 | 贵州师范大学 | Method for recycling carbonaceous materials in aluminum electrolysis carbon-containing waste |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112086703B (en) | 2021-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112086703B (en) | Resource treatment method for carbon residue of retired battery | |
| Zhao et al. | Regeneration and reutilization of cathode materials from spent lithium-ion batteries | |
| CN111129632B (en) | Method for recycling anode and cathode mixed materials of waste ternary lithium ion battery | |
| CN111463475B (en) | Method for selectively recycling waste power lithium battery positive electrode material | |
| CN110343864B (en) | Method for recovering lithium and cobalt in waste electrode material by microwave roasting assistance | |
| CN113258158B (en) | Treatment method for recycling waste lithium ion batteries | |
| CN112441572A (en) | Method for recovering waste lithium iron phosphate anode material | |
| CN112897492B (en) | Method for regenerating and recycling high-impurity lithium iron phosphate waste powder | |
| CN112047335B (en) | Combined treatment method for black powder of waste lithium ion battery | |
| CN113896211A (en) | Resource treatment method for waste lithium iron phosphate batteries | |
| CN112111651A (en) | Pyrogenic process recovery process of waste lithium ion battery powder | |
| CN113793994B (en) | Method for recycling waste lithium iron phosphate batteries | |
| CN114335781A (en) | Method for extracting precious metal from waste lithium battery | |
| JP2023530325A (en) | Cathode material recovery method | |
| CN114709504A (en) | Clean recovery method of waste lithium iron phosphate anode material | |
| CN110872648B (en) | Method for recovering valuable metals from waste ternary lithium ion battery positive electrode material | |
| CN114006067B (en) | Method and system for recycling anode and cathode mixed powder of waste ternary lithium ion battery | |
| CN115304059A (en) | Recycling treatment method for retired battery carbon slag | |
| CN114421042A (en) | Method for recovering metal aluminum, lithium carbonate and sodium nitrate from waste lithium iron phosphate material and application thereof | |
| CN114024049A (en) | Regeneration method of graphite cathode of waste cobalt acid lithium battery | |
| CN114950361B (en) | Method for preparing composite adsorbent through waste lithium batteries | |
| CN110523751B (en) | Method for recycling carbon substances in waste cathode leaching residues of aluminum electrolysis cell | |
| CN116639686A (en) | Method for preparing porous graphite from waste lithium ion battery carbon residues | |
| CN116605857A (en) | Impurity removal method for waste battery leaching liquid | |
| CN116282000A (en) | Method for recycling waste battery graphite carbon slag and co-producing regenerated graphite active material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |